1. In-Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química y Ambiental Rebeca Sánchez Vázquez I. A. Vasiliadou, Juan A. Melero, F. Martínez, L. Fernando Bautista, J. Iglesias, G. Morales and R. Molina

2. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental 1 st generation biodiesel Palm Oil Canola Oil Sunflower OilSoya Oil Castor Oil Jatropha Oil The biodiesel production process 1 st Generation Biodiesel

3. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Non-edible feedstock New technologies Non-food crops Algae oils Microbial oil Waste cooking oils Other waste 2 nd Generation Biodiesel Non-food / land for fuel Safer process Greener process Profitable process High purity by-products The biodiesel production process 2 nd Generation Biodiesel Waste animal fats

4. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Alternative source for oleaginous feedstock Wastes  Large amounts of non-saponifiable compounds Contact with water  High FFA contents due to hydrolysis processes ~ 1.6 MT produced yearly in the EU Increasing due to incresing urbanization and industrialization. ~ 10-30 wt% of lipids content Direct adsorption of lipids onto the sludge. Cell membrane of microorganisms composed of phospholipids Sewage sludges

5. Experimental

6. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Oil Extraction Solvents Diethyl Ether, n-Hexane and methanol Conditions Temperature: Boiling point of the solvent Solvent to Biomass:10 – 15 mL·g -1 Contact time: 2.5 and 4.0 hours Drying stage T = 80ºC P = 0.5 bar t = 12 hours Waterremoval Solvent refluxing T = Boiling Temp. P = atm. t = 2.5 – 4.0 hours Extraction of lipids Filtration Solidsremoval Evaporation T = 80ºC P = 0.2 bar Lipidsconcentration

7. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Zr-SBA-15 Zirconium species Isomorphic substitution Mesostructured silica as solid support High surface area. Large pore size. Lewis-type acid catalyst Zirconium & zirconium dioxide species Zr – SBA-15 Heterogeneous acid catalytic system Zr loading (wt. %): 8.4 S BET (m 2 /g): 556 V p (cm 3 /g): 1.35 D p (nm): 12.9 Si/Zr) EDX  20 Si/Zr) bulk –ICP  16 Si/Zr) XPS  18 High incorporation of Zr. Textural properties. Mesoscopic ordering.

8. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Temperature (ºC) Catalyst Loading (wt% on lipid mass) MeOH/Saponifiable Matter (mol/mol) 20912.550 Catalytic test Tryglicerides & free fatty acidsMethanol + Biodiesel + Glycerol Stirring rate: 2000 rpm Heating ramp:7ºC/min Autogenous pressure

9. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental 76543210 1 H d (ppm) CH 3 R… CH 2 CH 2 C O...R CH 2 CH 2 C O O CH 2 CH O CH 2 CH 2 C O CH 2 O CH 2 CH 2 C OOH CH 2 CH 2 C O Yield toward FAME: 1 H NMR

10. Results & Discussion

11. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Oil Extraction:Primary - Sewage Sludges n - Hexane Extraction Yield (wt%) Methanol Diethyl ether n-Hexane & methanol  Very good extraction yields Diethyl ether Very poor extraction yield. Discarded solvent. 15,0 12,5 10,0 7,5 5,0 2,5 0,0 Large amount of UnsaponifiableMatter and Free Fatty Acids obtained

12. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental % FFA % Gly Reaction Product (3h) 0 20 40 60 80 100 Molar composition (%) FAME Yield (%) 0 20 40 60 80 100 Reuse Product (3h) Reaction Product (6h) Transesterification reaction – Primary - Sewage Sludges Batch experiments H igh conversion of FFA and TG into FAME after 3h 6.0 % of the total sewage sludge is converted into FAME

13. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Transesterification reaction – Primary - Sewage Sludges In Situ Process Blank Reaction Product (3h) DB(g)/S(ml) = 0.1 Reaction Product (3h) Reaction Product (6h) Reuse Product (3h) RP (3h) Wet Sludge DB(g)/S(ml) = 0.25 H igh FAME yield from primary sewage sludge through In situ process H igh FAME yield from sewage sludge without drying treatment (72 wt% water content)

14. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental 15.5 % of the total sewage sludge is converted into FAME 5.8 % of the total sewage sludge is converted into FAME Conventional Process In Situ Process Transesterification reaction – Primary - Sewage Sludges

15. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Oil Extraction:Secondary - Sewage Sludges Extraction Yield (wt%) n-Hexane T he amount of extracted lipid from secondary sludge is much lower 3.0 2.5 2.0 1.5 1.0 0.5 0.0 G reater proportion of saponifiable matter and Free Fatty Acids obtained Methanol Composition (%) 62.3 20.7 16.9

16. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Transesterification reaction – Transesterification reaction – In Situ Process SecondaryPrimary World wide production ~ 20.000.000 T / año  ~ 4.000.000 T biodiesel

17. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Ganoderma Lucidum Trametes Versicolor Potential oil extraction capacity of Fungal biomass Fungal sludge generated during the bio-degradation process was used for biodiesel production by means of one-step direct transformation. Removal of emerging pharmaceutical pollutants Alternative biological cultures: White-rot fungi in suspended growth medium with remarkable removal efficiency.

18. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Oil Extraction:Ganoderma Lucidum and Trametes Versicolor Extraction Yield (wt%) 2.5 h 100 ml Methanol Remarkable extraction yield Composition (%) Large amount of glycerides and Free Fatty Acids obtained

19. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Transesterification reaction – In-Situ Process H igh FAME yield from fungy biomass through In-situ process. % FFA % Gly Reaction Product (3h) Reuse Product (3h) Reaction Product (3h) Reuse Product (3h) Trametes Versicolor Ganoderma Lucidum

20. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Trametes Versicolor Ganoderma Lucidum Transesterification reaction – In-Situ Process

21. Conclusions

22. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental Fungus and Sewage Sludge from the primary and secondary treatment unit in waste water treatment plants can be used as alternative feedstock for biodiesel production. Extracted highly acidic impure oils can be easily converted into FAME by methanolysis in presence of the highly stable heterogeneous acid catalyst Zr- SBA-15. The extraction and conversion into FAME of the lipids contained by Sewage Sludge and fungus can be accomplished in a single step in presence of heterogeneous acid catalysts yielding better results than aplying both techniques separately. Conclusions

23. In- Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química Y Ambiental FINANCIAL SUPPORT FROM IS GRATEFULLY ACKNOWLEDGED Dr. I. Vasileiadou Dr. J. A. Melero Dr. F. Martínez Dr. F. Bautista Dr. J. Iglesias Dr. G. Morales Dr. R. Molina CTQ 2008-01396 S-2009/ENE-1743

24. In-Situ Transformation of Municipal Sewage Sludge into Biodiesel Grupo de Ingeniería Química y Ambiental Rebeca Sánchez Vázquez I. A. Vasiliadou, Juan A. Melero, F. Martínez, L. Fernando Bautista, J. Iglesias, G. Morales and R. Molina